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Patented June 15, 1943 POLYMERIC MATERIAL (Henry S. Rothroclawiimington, Del.,'-assignor to 'I-I E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawint. ADDHcationOctoberM, A SerialNo.361,188

v I i v 4Claims. -(Cl. gee- 7 i This. invention relates to new compositions of matter and more particularly to polymeric ma -terials. Previous. attempts to obtain polymeric and.

resinous materials suitable for. coating compositions through the polymerization ofjestersi'of unsaturated alcohols with unsaturated polycarable take-om 1940, f yan solved 111x100 .cc. of methanol and over a;,per io d of two hours 10 cc. of -the catalyst solution,was

added. -The rate of'additionofgthe catalyst ;,was adjusted 'so as;tomaintaintheiinterchange re 7 'actionat a uniform-rate. I The ethanol liberated; by the reaction-was .removed by dis tillat ion 8 1i f freslrbenzeneiwas added tothe reaction mixture boxylic acids has beenconflned to the polymer 7 ization of esters obtained from unsaturated alcor,

hols in which the carbinol group is attachedfto an unsaturated'atom.

This invention has as an object the production 4 of new and useful compositions of matter, A

from 'timeitoftime" toireplace that-.whichdistilled ofi.""-The'=- reaction :was complete in- -tabout five;

"hOlll'Sfi The product was thoroughly washedwith water,-;the benzene removed by distillation and; finally the :mixture was distilled underreduced 1 pressure. Some material (28 g.) whichboiled at further object is the manufacture of new'polymeric andresinous materials. A still further obv ject is the production of new and improved. coating compositions. Otherobjectswill appea V hereinafter.

These objects are accomplished by formingd polymers from esters of polycarboxylicacids and unsaturated alcohols, in which alcohols the'carblnol group is attached only to saturated carbon atoms, said polymerization being carried out' in the presence of catalysts as hereinafterhde-h scribedyand preferably in thin films in the presence of a metallic drier whereby superior hard, flexible, light-colored films are obtained.

Alcohols: useful in making the esters from which the polymers of this invention are ob.-

tained include allyl carbinol, China-wood oil 'ai-I cohol which is-prepared by sodium reduction oi the methyl esters of China-wood oil acids, and other unsaturated alcohols referred to hereinafter in which the carbinol group is attached only to saturated atoms.

The polymerization of the unsaturated" acid esters of the above mentioned unsaturated alco-fl hols can be efiected in the presenceof a suitable catalyst at room temperatures up to'200 C.

or more-depending-upon the particular ester used. In the preferred practice of this invention the esters are treated with cobalt drier, or

other metallic organic compound capable oi hardening the films of unsaturated oils, and the ester polymerized directly in the film. Intermediate polymerized esters resembling bodied natural drying oils can be obtained by preliminary heating of the ester,

: The invention is further illustrated by the following examples:

Example I A mixture of 133 g. (0.5 mol) of China-wood oil alcohol, 44.4,g. (0.2 mol) of ethyl maleate. and 200 g. of dry benzene was heated at reflux under an efllcient columnequipped with avari- 185-190? '2./3 was presumably China-:woodjoil alcohol. I Theresidue, consistingotphlnas-wood r oil alcohol maleate' weighedd'lz g." Afterfthead; dition of.. 0'.03 of: cobalt as cobalt naphthenate r- .to' -this"ester, a; film. of the composition air-dried ;in 'one'= hour: tack-free, and baked dry in, 15, minutegat'lOOfiC' -U sing.a procedure similar mpx mmer 43g. v (0.5-mol) of methal lyllcarbinol, 34g. (0.2m'ol). i s ethyl i'umarata and 300 g...o'f Ibenzen'etcgether with 28 cc; of sodium methylate catalyst;Jsolt'ition l prepared as in Examplel wa's'allowed to react for-five and one-half hour-sand wasworked'u'p in a similar rasmj lii yielding, 12 0 fggor methallyl c lbinolfurnarate. boiling at 15 Q.}-.1 8 7 f "C./4" This material set up to a tat-k4ree film inforieand oneduarter hours at 1-00..C.Iin the, presence I of 0.03% cobalt in tneg'roii or; cobalt "naphthenate, p .1 "1,

. Example)! In a mannersimila'rto that offlEXample I, a mixture of 34.4 g. (o'.2 mo1 or,ethy1 'iumarateg 107.2 g. (0.4:m'o'l) ofoleyl alcoholand'250 cc oi' r benzene with 30cc. of sodiummethyiate-catalyst solution prepared as in Example I was allowed to react for five hours. The reaction mixture was then washed with acidified water and the" benzene as removed on a water bath*under reduced pressure. The residue, chieflyoleyl fum- ,arate, weighed. 100 g. This compound when treated with 0.03% cobalt as cobalt naphthenate and baked at 100 C. for 24 hours gavea tacktough, perfectly dry film.

The polymerizedveste'rs of the present invention" free In 72 hours, it had baked to a very can be obtained from a large varietyoflunsaturated alcohols in addition to those mentioned inthe examples.

Five grams 30i was also as molding compositions.

2 Further compounds of this type are citronellol,

I allyl carbinol; 3-pentynol,

Aliphatic, hydroaromatic, or aromatic polycarboxylic acids can be used in making the polymerized esters of this invention. Suitable acids.

include maleic acid, fumaric acid, itaconic acid,

thinners by any of the methods known vinyl malonic acid, citraconic acid, aeonitic acid,

tetrahydrophthalic acid, 1,2'-dihydronaphthalene- 3,4-dicarboxylic acid, adipic acid, sebacicracid,

phthalic acid, 1,4-dihydronaphthalene-2,3-dicarboxylic acid, tricarballylic acid, and the like.

The metallic drier catalysts of the preferred type arei-the cobalt, manganese, and lead salts of naphthenic and linoleic acids which are soluble in organic solvents and which are commonly used to catalyze the hardening or set-up" of natural drying oils. The cobalt salts are usually added in proportionsto make about 0.03% cobalt based on the unsaturated ester and from 0.01 to i 0.1% may beused. With the lead'salts usually sufficient to make about 1.0% of lead based on.

the unsaturated ester is preferredalthough from 0.1 to 2.0% may be used.. With the manganese salts usually 0.1% .oi'manganese based on the. unsaturated ester is preferred and from 0.03 to 0.2% may be used. Other metals, the naphthenic and-lino1eic acid salts of which are somewhat useful in this'capacity are iron, vanadium, copprises heating in the presence of a metallic drier.

per, and cerium. Insomeinstan'ces the'lmetallic.

drier catalyst'may be replaced by .orq gen-llielding catalysts such as benzoyl peroxide,:lauroyl peroxide, acetyl peroxide and peracetic acid.

Polymerization of the esters may age carried out alone to produce a varnish or maybe admixed with pigments o'r plasticizersr letc; to produce enamels and other types of coating compositions.

Instead of using the pure ester itself, it is some-' times desirable to use mixturesof the present esters or one of these esters and otherpolymerizable unsaturated compound to'for'm interpolymers. Thus valuable interpolymers useful in coating and molding are obtained in thismanner from other unsaturated compounds such as vinyl esters, acrylic and methacrylic esters, and styrene. A new class of materials which are useful as vehicle for improved air-drying or baking coating, impregnating, or adhesive compositions and For these uses,

they can be formulated with Pigments, metallic driers, fillers, waxes, inhibitors, plasticizers, and

in the art. Useful coating compositions can also be 1 made from these esters in combination with other film-iorming materials such as, for example, drying oils, drying oil varnishes, cellulose acetate. cellulose nitrate, chlorinated rubber and soluble phenol-formaldehyde or urea-formaldehyde resins. When these film-forming materials are used it is sometimes preferable to mix these esters with the other material, subject to a preliminary bodying action and then used as a coating composi tion. The products of the present invention, with or without the above-noted auxiliary film-forming and other materials, can be used with metals or wood, directlyor over suitable base coats, and

they can also be used over glass, leather, stone, cloth, paper, rubber, or cellulose, the form of the' substrate being immaterial. The products of this invention are useful for molding into any desired form. In addition, theycan be prepared in the shape or unsupported films or sheetlngs. The latter can be employed for a variety of purposes such as for safety glass interlayers, wrapping foils, and

the like.

Asm'any' apparently widely different embodiments of' this invention may be made without departing from the spirit and scope thereof, it is to beunderstood that I do not limit myseli to the specific embodiments thereof except as,de-

fined in the appended claims.

I claim: ;1. A process for making polymers which coman ester of an unsaturated polycarboxylic acid and an acyclic and completely aliphatic mono unsaturated monohydric alcohol in which all the carboxylic groupsare esterifled by said alcohol,

and in which the carbinol group i attached only to a saturated carbon atom.

- 2. A'process for making polymers which comprises heating at about 100 C. in the presence of a metallic drier an ester of an unsaturated polycarboxylic acid and an acyclic and completely aliphatic monounsaturated monohydric alcohol in which all the carboxylic groups are esteriiled by said alcohol, and in which the carbinol group is attached only to a saturated carbon atom. 1 3. A process for making polymers which comprises heating at about 100 0. with cobalt drier HENRY S. RO'I'HROCK. 

